Method of incorporating metal complexes in a base oil



* atent ice 3,055,828 METHOD OF INCORPORATING METAL COMPLEXES IN A BASE OIL Morris A. Wiley, Fishkiil, N.Y., assignor to Texaco Inc, a corporation of Delaware No Drawing. Filed July 7, 1958, Ser. No. 746,645 11 Claims. (Cl. 252-18) This invention relates to a method of incorporating metal complexes in a base oil to form concentrates useful 7 as additives for lubricating and fuel preparations.

In copending, coassigned application, Serial No. 645,- 667, filed March 13, 1957, by Herman D. Kluge, Morris A. Wiley and Kenneth L. Kreuz, now abandoned, a method of incorporating metal compounds in oils is disclosed wherein a metal base, a dispersant and an oil are heated together at a temperature of from 250 to 450 F. with oxygen blowing for a number of hours and then heated to a temperature at least 50 F. higher with continued oxygen blowing for several hours to obtain the desired product.

In copending, coassigned application Serial No. 747,- 089 filed of even; date herewith by Morris A. Wiley and Herman D. Kluge, an inorganic metal base, a metal carboxylate and a dispersant are heated in a lubricating oil at from 400 to 850 F. for a given length of time under non-oxidizing conditions to obtain the desired product.

The processes of the copending applications and that to be presently set forth incorporate substantial amounts of dispersed metal compounds in a base oil at relatively low cost per unit of added metal and permit excellent control of the amount of metal finally present in the product.

In accordance with the present invention the method of forming metal complex-containing concentrates comprises heating a metal carboxylate, a basic reacting inorganic metal compound in a lubricating oil in the presence of a dispersant at a temperature ranging from 325 to 550 F., blowing with an oxygen-containing gas during said heating for a time sufficient to effect decomposition of the carboxylate and to obtain a concentrate containing a dis persant, metal carboxylate and the dispersed products of the decomposition of metal carboxylate.

The process of the present invention differs primarily from that of application Ser. No. 645,667 in that the car'- boxylic acid or metal carboxylate is added initially with the charge material thus enabling better control of the carbonate and carboxylate present in the product.

The present method is advantageous in that decomposition of the carboxylate occurs at lower temperatures than are attainable Without oxygen blowing. v

In a preferred form of the invention, a carboxylic acid material, a dispersant precursor acid and the inorganic basic metal compound are mixed in a lubricating oil base and saponified and neutralized at a temperature ranging from 125 to 250 F. and preferably from 180 to 220 F. The reaction mixture may suitably comprise about 2-40 percent by Weight of carboxylic acid material, about 1-30 percent by Weight of inorganic basic metal compound, about 1-40 percent by weight of a dispersant precursor acid material and about 30-90 percent by weight of lubricating oil. Very advantageously, the mixture comprises about 2-20 percent by weight of carboxylic acid material,

about 4-20 percent by weight of the dispersant precursor material, and about 50-75 percent by weight of lubricating oil. The time for saponification at these temperatures ranges from 5 minutes to 4 hours and preferably from. 1 to 2 hours. Thus, the metal carboxylate and dispersant are formed in situ and the mixture is then subjected to higher temperature of from 325 to 550 F. and preferaJbly from 400 to 500 F. while blowing with an oxygen containing gas during said heating for a time period ranging from 5 minutes to 8 hours and preferably from 30 minutes to 2 hours to effect decomposition of the carboxylate and to obtain a concentrate containing a dispersant, metal carboxylate and dispersed product of the decomposition of metal carboxylate.

The oxygen containing gas mentioned above is conventionally air. However, pure oxygen, ozone, or mixture of oxygen and other gas wherein the oxygen is present in amounts sufiicient to cause oxidation under the temperature and time limitations outlined for the process of this invention are useful. The rate of air blowing is generally from 0.5 to 5 liters per minute through from 0.5 to 5 liters of the mixture in the reacting vessel. Preferably the rate of air blowing is from 1 to 2 liters per minutes per liter of reaction mixture.

The dispersants used in the method of this invention are metal salts of organic acids having high solubility in lubricating oils and which must be heat stable at temperatures of at least 350 F. and preferably as high as 600 F. Examples of the dispersants include normal, basic and superbased oil soluble petroleum (mahogany) sulfonates. Synthetic sulfonates such as alkyl aryl sulfonates derived from alkylated benzene or naphthalene may be used. Other useful dispersants include metal alkyl phenolates or sulfurized alkyl phenolates, the alkyl groups in each case having at least 8 carbon atoms, and advantageously from 8 to 60 carbon atoms; salts of alkyl phenol-formaldehyde condensation products; salts of hexamethylene tetramine-alkyl phenol condensation products; naphthenates and naphthenic acids; and the metal salts of olefin-phosphorus sulfide reaction products wherein the olefin has a molecular weight ranging from 400 to 10,000.

The dispersant per se may be added prior to the initial saponification step or added just prior to the elevated temperature oxidation procedure. However, as previously stated the dispersant is preferably formed in situ by adding the dispersant precursor acid to the mixture prior to saponification. For example, a sulfonic acid, naphthenic acid, olefin-P 8 product, alkyl phenol or derivative thereof is heated in the presence of the basic reacting inorganic compound to form the metal salt at about the same time the metal carboxylate is formed in the process of the invention.

The amount of the dispersant used is dependent on the amount of metal compounds to be dispersed in the coin centrate. Generally, the amount of dispersant used is from 1.0 to 40.0 (mol) percent and preferably 4.0 to 20.0 (mol) percent of the stoichiometric quantity of the metal employed in this process.

Preferred dispersants for this invention include oil soluble metal petroleum 'sulfonate's made from a sulfonic acid having a molecular weight of about 350 to 450 and the metal salt of a polyisobutylene P S reaction prod= 3 not wherein the polyisobutylene has an average molecular weight of from 700900.

The carboxylic acids used in the process of this invention include aliphatic monocarboxylic acids, for example, formic, acetic, propionic, acrylic, butyric, valeric, sorbic, capric, caproleic, lauric, myristoleic, palmitic, oleic, stearic, vaccenic, linoleic, linolenic, behenic, cerotic, montanic, melissic, naphthenic and chaulmoorgric acids. Carboxylic acids containing other functional groups are useful. These include, for example, hydroxy carboxylic acids such as lactic, 2-hydroxycaprylic, 2-hydroxylauric, 16-hydroxypalmitic, 12-hydroxystearic, 11,12-dihydroxystearic, lanoceric, and ricinoleic acid. This group also includes keto-carboxylic acids such as pyruvic, acetoacetic, 4-ketocaproic, 2-ketolauric, 9-ketostearic and IO-ketobehenic acid. Dicarboxylic acids are also used; examples of such acids are malonic, maleic, succinic, itaconic, adipic, suberic, azelaic, sebacic and eicosanedioic acid. The aromatic and substituted aromatic carboxylic acids are in a like manner useful materials for this invention. Some examples are benzoic, salicylic, alkylsalicyclic, tropic, phthalic and divaric acid.

Acidic materials produced by oxidation of organic compounds are other useful materials for this invention and are at times preferred because they are inexpensive and easily obtainable. Theses products include oxidized mineral oils, acid type wax oxidates, overhead condensates from oxidation processes, distilled fractions of oxidates, naphtha soluble fractions of oxidates, etc. Not to be omitted from the useful carboxylic acid-containing materials are the naturally occurring fatty materials, such as lard, vegetable oils, animal residues, and glycerides. In some instances, other organic materials such as esters, amides and the like are suitable sources of acid radicals.

Both economic considerations and quality of product dictate a preference for low molecular weight aliphatic carboxylic acids, particularly formic and acetic acids, and for acidic material produced by oxidation of mineral oils; wax, etc., as a carboxylic acid material for use in this invention.

The amount of carboxylic acid which is used in the process of this invention is such as to provide a metal complex containing concentrate having dispersed therein from 0.1-15 weight percent of metal carbonate, 1-40 weight percent dispersant, and 0.5-30 weight percent metal carboxylate; the metal being present in the oil in an amount of at least 1.0 weight percent and not exceeding 25 percent. As a practical matter the carboxylic acid usually constitutes from to 50 (wt.) percent of the reaction mixture and preferably from to 35 (wt.) percent.

The basic reacting inorganic metal compounds which are useful for this invention include the oxides, hydroxides and carbonates of alkali metals, the alkaline earth metals, lead, tin and Zinc. The preferred metal compounds based on their comparative usefulness in the process of the invention are the oxides and hydroxides of barium, calcium and lead.

The amount of the metal compound which is effectively employed in the process of this invention is dependent on the amount of acid material employed in the initial step of the process. The metal compound should at least be present in an amount in excess of the stoichiometric quantity theoretically required for neutralization and saponifi cation of the carboxylic acid compound and other acidic materials present. Generally, amounts of at least about 10 percent and particularly within the range of from to 400 percent in excess are applicable. Preferably, the metal compound should be present in the amount of about 50 to 200 (wt.) percent in excess of the stoichiometric quantity theoretically required to completely saponify the carboxylic acid, its derivatives, or other acidic material present. When excess amounts, for example from 200 to 400 percent of basic metal compound are used above that theoretically required to completely saponify the carboxylic acid or its derivatives, greater amounts of previously described dispersant material should be employed. In general, the use of an excess of the metal is desirable for promoting high metal content and alkalinity to the product.

Water is desirably employed in the reaction to promote saponification and reactiveness of the metal base compounds. Generally, about 1.0 to 30 (wt.) percent of water based on Weight of the charge materials were found helpful and preferably 5.0 to 10 percent of water was used.

The base oils which are used in the process of this invention are hydrocarbon oils both of the natural and synthetic type. Naphthene, parafiin and residual type mineral lubricating oils, and mixtures thereof are normally employed. These oils include those which have been subjected to all types of refining techniques including solvent refining, dewaxing and hydrorefining. Synthetic base fluids such as high molecular weight polybutenes are also included.

As previously disclosed, saponification is preferably made to take place separately in order to form the carboxylate and dispersant in situ prior to the reaction at higher temperatures with oxygen blowing. It is frequently desirable to introduce a solvent such as water or petroleum hydrocarbon, such as heptane, to promote ease of saponification.

To finish the metal complex containing concentrates of the invention they are generally filtered to remove excess solids thereafter obtaining clear, filterable and stable complexes.

At times, in order to convert any remaining metal oxide or hydroxide still present in the complex, or dispersed in colloidal form, to a neutral salt, the product is carbon dioxide blown at about 450 F., conveniently at 250 to 350 F. for about five minutes to four hours. Other acidic gases such as hydrogen sulfide or sulfur dioxide may be employed to obtain a neutral product.

The metal complex is an excellent detergent additive for hydrocarbon compositions notably lubricants. It is generally incorporated in lubricants in amounts wherein the metal compound content is from 0.1 to 5 percent by Weight of the total lubricant composition.

The metal complex additives prepared in accordance with this invention are effective detergent additives for crankcase lubricants employed in internal combustion engines. They are especially useful as alkaline additives for cylinder lubricants for diesel engines operating on low quality distillate or residual fuels. Such fuels often contain high amounts of sulfur, vanadium and other materials normally corrosive to metal engine parts, particularly rings and liners. These metal complexes, particularly the alkaline earth metal derivatives, are effective in controlling deposits and in preventing the usually high rates of corrosive Wear normally associated with the use of low quality fuels in diesel engines.

The selection of the metal base employed for preparation of the metal complex in accordance with this invention depends upon the intended use for the lubricant in which the metal complex is incorporated. For lubrication of gears, extreme pressure properties may be more important than dispersant and detergent properties. In this case the metal complex would normally be prepared from a lead oxide in order to impart extreme pressure properties to the lubricant.

Examples of the process of this invention are given as follows:

EXAMPLE I 98 g. of a refined oxidate from a furfural refined, light acid treated, clay contacted and solvent dewaxed parafiin base wax distillate were charged to a reaction vessel. The crude oxidate from which this refined material was derived was prepared by the method set forth in copending, coassigned application Serial No. 710,856, filed January 24, 1958, now US. Patent No. 2,978,472 by George B. Kirkwood and John H. Greene. In accordance with this method the refined paraffinic oil is reacted with air in the presence of a metalliferous oxidation catalyst. The preferred conditions include an air feed rate of -25 cu. ft. per lbs. oil per hour, an air velocity of about 0.2-1 ft. per sec., an oxidation initiation temperature of 330-370 R, an oxidation reaction temperature of 260-300 F., a reaction pressure of 50-90 p.s.i.g. and a potassium permanganate catalyst in an amount of 0.4 to 1.2 percent by weight based on the charge oil. Oxidation is continued to a neutralization No. of between 55 and 70.

The refined oxidate was obtained by washing crude oxidate with a 40 percent solution of H 80 in water at about 140 F. and then with water at about 150 F. The purpose of the sulfuric acid and water washes was to remove any metal present as metal naphthenates. These metal naphthenates originate from the transition metal catalyst employed in the preparation of the petroleum oxidate. The oxidate was then dried by nitrogen blowing at 210 F. The refined oxidate had a saponification No. or" 108, a neut. No. of 28.2 and a calculated combining weight of approximately 520 g. on the basis of the sap. No. 141 g. of a petroleum sulfonic acid having a neut. No. of 36.4 in a mineral oil carrier, 245 g. of isoheptane as a solvent for the sulfonic acid concentrate, 261 g. of a refined paraflin base distillate oil having a gravity API of 31.6 and a viscosity SSU at 100 F. of 155, 77 g. of barium oxide and 9 ml. of water were also charged to the reaction vessel. Isoheptane is a petroleum solvent of the approximate boiling range of a mixture of heptanes. It is a useful solvent which can be readily stripped from the reaction mixture by distillation.

The indicated calculated stoichiometn'c ratios for each of the reaction components of the mixture were as follows:

Table l Barium oxide 1.00 (basis theoretical combining wt.).

Oxidate 0.19 (basis sap. No.).

Sulfonic acid 0.25 (basis neut. No.).

The reaction mixture was refluxed at a temperature of 195 F. with stirring for a period of 2 hours. The mixture was then blown with 1.0 liter of nitrogen per minute and heated to 420 F. to remove the solvents. On reaching 420 F. the mixture was cooled to 250 F. and then reheated to 450 F. while blowing with air at the rate of 2.0 liters per minute. The mixture was kept at a temperature of 450 F. for 2 hours with continued air blowing. After 2 hours the mass was filtered. This concentrate was fluid, stable and filterable. A blend of 5 wt. percent of the concentrate in an SAE 10 grade mineral oil was clear and bright, demonstrating the oil solubility of this concentrate.

The concentrate product showed the following test results:

Table II Ba, percent 11.7 CO percent 1.29 Neut. No .67

It was calculated that 34 percent of the total barium was present as dispersed barium carbonate, basis carbon dioxide analysis.

EXAMPLE II Table III Barium oxide 1.0 (basis theoretical combining wt.). Oxidate 0.2 (basis sap. No.).

Formic acid; 0.2 Sulfonic acid 0.5 (basis neut. No.).

The reaction mixture was refluxed for 1 hour at 195 F. with stirring. The mixture was then blown with air at a rate of 2.0 liters per minute while heated to 450 F. and for 2 hours at that temperature. The product was then filtered.

The following table demonstrates the eifect of the length of time of oxidation of the mass with products of this example.

An improvement in metal content is seen with the length of time of oxidation.

EXAMPLE III 104 g. of the refined oxidate of Example I, 53.2 g. of petroleum sulfonic acid in a mineral oil carrier and 92 g. of isoheptane of Example I, 22.4 g. of calcium oxide, 36 ml. of water, and 359 g. of a refined naphthene base distillate oil having a gravity, API of 18.4 and a viscosity SSU at F. of 1663, were charged to a reaction vessel.

The stoichiometric ratios of the reaction components were as follows:

Table V Calcium oxide 1.0 (basis theoretical combining wt.). Oxidate 0.25 (basis sap. No.). Sulfo'nic acid 0.11 (basis neut. No.).

After refluxing for 2 hours with stirring at a temperature of 195 F. the mixture was blown with air at the rate of 2.0 liters per minute while the temperature was raised to 450 F. Air blowing was continued at this temperature for 1 hour and then the mixture was filtered to produce a bright product.

Testing of the product of this example produced the results given in the following table:

Table VI Ca, percent 2.47

CO percent 1.00 Neut.No .33

It was calculated, basis carbon dioxide analysis, that 37 percent of the calcium was present as dispersed calcium carbonate.

EXAMPLE IV 51 g. of a refined ester type parafiin wax oxidate having a saponification No. of 139, a neutralization No. of 78.7 and a calculated molecular weight of 403 were charged to the reaction vessel. The oxidate was prepared in accordance with the method set forth in copending, coassigned application S.N. 712,073, filed January 30, 1958, now US. Patent No. 2,894,970 by John K. McKinley, Roy F. Nelson and Gordon S. Bright. The wax oxidate was refined by washing an ether solution of the crude oxidate with 20 wt. percent of a 40 percent H 80 solution and then with water at F The ether was then evaporated on a steam plate.

242 g. of the refined naphthene base distillate oil of Example III, 20 g. of petroleum sulfonic acid in a mineral oil carrier and 34 g. of isoheptane of Example I, 18 ml. of water, and 11.2 g. of calcium oxide were also charged to the reaction vessel.

The mixture was refluxed for 2 hours with stirring at 195 F. After refluxing the mixture was blown with air at the rate of 1.0 liter per minute at 450 F. for 30 minutes. After the first 15 minutes of blowing, 11.2 g. additional calcium oxide was added.

The stoichiometric ratios of the reactants are given in the following table:

Table VI] Calcium oxide (1st addition) 1.0 Calcium oxide (2nd addition) 1.0 Oxidate 0.25 Sulfonic acid-" 0.07

A sample of the preparation was taken when the temperature of the mixture reached 350 F. and another sample taken when 450 F. was reached. These samples along with a sample of the product after completion of the process were filtered and analysed. The test results are given in the following table:

The finished product had greater metal content and more alkalinity, as dispersed calcium carbonate, compared to the intermediate samples with less oxidation time.

EXAMPLE V 102 g. of refined ester type wax oxidate having a saponification No. of 190, a neutralization No. of 84.8 and a molecular weight basis sap. No. of 295 were charged to the reaction vessel. This oxidate was prepared in accordance with the disclosure of application S.N. 712,073 mentioned in Example III. The crude oxidate was refined by dissolving in ethyl ether, extracting with 20 (wt.) percent of 40 percent H 50 then extracting several times with water, evaporating the ether on a steam plate and again washing several times with hot water (ISO-190 F.)

40 g. of petroleum sulfonic acid in a mineral oil carrier, 68 g. of isoheptane of Example I as a solvent for the sulfonic acid concentrate, 22.4 g. of calcium oxide, 36 ml. of water and 375 g. of the refined naphthene base distillate oil of Example III were also charged to the reaction vessel.

The stoichiometric ratio of the reactants of the mixture are given in the following table:

' Table IX Calcium oxide 1.0 Oxidate 0.5 Sulfonic acid 0.18

Table X Ca, percent 2.1 1. CO percent 0.30. Neut. No 8.32 (alk.).

It was calculated, basis carbon dioxide analysis, that 13 percent of the calcium was present as calcium carbonate. It was calculated, basis neutralization Number,

that 14 percent of the calcium was present as dispersed calcium hydroxide.

EXAMPLE VI 51 g. of a refined wax oxidate of Example V, 20 g. of a petroleum sulfonic acid in a mineral oil carrier, 34 g. of isoheptane of Example I as a solvent for the sulfonic acid concentrate, 23.9 g. of lead oxide, 18 ml. of water and 121 g. of the refined naphthene base distillate oil of Example III were charged to a reaction vessel.

The stoichiometric ratios of the reactants is given in the following table:

Table XI Lead oxide (PbO) 1.0 Oxidate 0.5 Sulfonic acid 0.18

The mixture was stirred for 2 hours with refluxing at F. after which it was blown with air at a rate of 1.0 liter per minute while the reaction temperature was raised to 400 F. and for 30 minutes at 400 F.

A sample of the mixture was taken when the temperature reached 400 F. and another when the process was completed. Each sample was filtered and analysed. The test results are given in the following table:

Table XII Sample at Finished 400 F. Product Lead, percent 9.12 9. 54 002, percent 0.03 0.1

EXAMPLE VII 104 g. of the refined oxidate of Example I, 38 g. of petroleum sulfonic acid in a mineral oil carrier and 65 g. of isoheptane of Example I as a solvent for the sulfonic acid concentrate, 44.6 g. of lead oxide, 36 ml. of water and 231 g. of the refined naphthene base distillate oil of Example III were charged to the reaction vessel.

The stoichiometric ratios of the reactants are given in the following table:

Table XIII Lead oxide (PbO) 1.0 Oxidate 0.5 Sulfonic acid 0.17

The mixture in the reaction vessel was refluxed for 2 hours with stirring at 195 F. After the refluxing procedure the mixture Was blown with air at the rate of 1.0 liter per minute while heating to 400 F. and for 5 minutes at 400 F. The product was filtered to obtain a clear, bright concentrate.

Test results on the product of this example are as follows:

Table XIV Lead, percent 9.6 EXAMPLE VIII Table XV Lead oxide (PbO) 1.0 Oxidate 0.5 Sulfonic acid 0.17

The mixture in the reacting vessel was saponified by refluxing for 2 hours at 195 F. with stirring. Thereafter, the mixture was oxidized by blowing with air at the rate of 1.0 liter per mintute while heating to 400 F. and for 5 minutes at 400 F. The product was filtered and analysed to give the following results:

Table XVI Lead, percent 8.98. Neut. No. (oxalate method) 4.9 (alkaline).

In Example VI it can be seen that little, if any, lead carbonate was present in the product, however, substantial amounts of lead were still incorporated in the base oil by following the process of this invention.

As can be seen by comparison of all the examples, the amounts of the components of a charge of materials to be reacted in accordance with the process of the invention may be varied over a considerable range without departing from the spirit and scope of the invention. In general, the ratios of amounts of materials charged will be governed by several considerations of operability, practicality, economics and quality of product for the applications intended. Among these considerations is the desirability of adjusting the materials charge so as to incorporate the maximum amount of metal possible in the final product, without rendering the reaction mixtures so viscous as to cause difficulties in processing, in order to eifect the most economical utilization of re actor vessels, filters, tankage and other accessory equipment. Another consideration is to use the minimum amount of the relatively costly dispersant or dispersant precursor consistent with quality of the final product as a detergent additive and consistent with obtaining a stable additive of high metal content. Another consideration is to employ minimum levels of acidic components, consistent with achieving a high metal content in the product, in order that the final product will have excess alkalinity capable of neutralizing acidic materials normally encountered in service operation of a lubricating oil in an internal combustion engine. Another consideration is a desire to utilize relatively low cost low molecular weigh-t carboxylic acids such as formic acid to the maximum extent to which they can be substituted for the higher molecular weight acids which are generally more costly on an equivalent combining weight basis.

Obviously, many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. A process for preparing a detergent concentrate which comprises providing a mixture consisting essentially of a hydrocarbon lubricating oil containing a metal salt of a material chosen from the class consisting of aliphatic monocarboxylic acids and saponifiable petroleum oxidates in an amount sufiicient to give about 5-50 percent by weight of the said material in the said mixture, about 1-40 percent by weight of an oil-soluble dispersant, and a basic reacting metal compound selected from the group consisting of metal oxides, hydroxides and carbonates in an amount sufiicient to provide about -400 percent of additional metal in the said mixture, heating the said mixture at a temperature in the range from 350 F. to 550 F. while blowing with an oxygen-containing gas for a period from 5 minutes to 8 hours until an alkaline reacting stable dispersion containing 'a substantially increased amount of metal is obtained, and thereafter cooling the reaction product and removing any undispersed solid material, said dispersant being selected from the group consisting of metal sulfonates, metal salts of olefin-phosphorus sulfide reaction products and metal alkyl phenolates, said metal salt, said basic reacting metal compound and said dispersant having their metal components selected from the class consisting of alkali metals, alkaline earth metals, lead, tin and zinc.

2. The process according to claim 1 wherein the said mixture is heated in the range 400-550 F. for a period of from five minutes to about four hours while blowing with air at a rate of 0.1-10 liters of air per minute per liter of the said mixture.

3. The process according to claim 1 wherein the said metal component is calcium.

4. The process according to claim 1 wherein the said metal component is barium.

5. The process according to claim 1 wherein the said metal component is lead.

6. A process for preparing a detergent concentrate which comprises providing a mixture consisting essentially of a mineral lubricating oil containing about 2-40 percent by weight of a saponifiable petroleum oxidate, about 4-20 percent by weight of a dispersant precursor material selected from the group consisting of sulfonic acids, olefinphosphorus sulfide reaction products and alkyl phenols, a basic reacting metal compound in an amount suflicient to give an excess of about 10 to 400 percent of the amount theoretically required to saponify and neutralize said carboxylic acid material and said dispersant precursor material, and about 1-3() percent by weight of water, heating said mixture at a temperature in about the range -250 F. for a time sufiicient to substantially complete all saponification and neutralization reactions, thereafter dehydrating the said mixture, further heating the mixture at a temperature in the range 350- 550 F. for a period from about 30 minutes to about 2 hours while blowing with air at a rate of about l-10 liters of air per minute per liter of the said mixture, and finally cooling the resulting product and separating any undispersed solid material therefrom, said basic reacting metal compound being selected from the group consisting of oxides, hydroxides and carbonates of alkali metals, alkaline earth metals, lead, tin and zinc.

7. The process according to claim 6 wherein the said product is finished by blowing with an acidic gas selected from the group consisting of carbon dioxide and sulfur dioxide at a temperature in about the range 450 F. for a period from about 15 minutes to about 4 hours.

8. The process according to claim 6 wherein the said dispersant precursor material is a petroleum sulfonic acid.

9. The process according to claim 6 wherein the said metal is calcium.

10. The process according to claim 6 wherein the said metal is barium.

11. The process according to claim 6 wherein the said metal is lead.

References Cited in the file of this patent UNITED STATES PATENTS 2,417,428 McLennan Mar. 18, 1947 2,417,433 McLennan Mar. 18, 1947 2,739,124 Otto et al. Mar. 20, 1956 2,739,125 Myers et al. Mar. 20, 1956 2,763,615 Faust Sept. 18, 1956 2,779,784 Sharrah Jan. 29, 1957 2,895,978 Brooks July 21, 1959 

1. A PROCESS FOR PREPARING A DETERGENT CONCENTRATE WHICH COMPRISES PROVIDING A MIXTURE CONSISTING ESSENTIALLY OF A HYDROCARBON LUBRICATING OIL CONTAINING A METAL SALT OF A MATERIAL CHOSEN FROM THE CLASS CONSISTING OF ALIPHATIC MONOCARBOXYLIC ACIDS AND SAPONIFIABLE PETROLEUM OXIDATES IN AN AMOUNT SUFFICIENT TO GIVE ABOUT 5-50 PERCENT BY WEIGHT OF THE SAID MATERIAL IN THE SAID MIXTURE, ABOUT 1-40 PERCENT BY WEIGHT OF AN OIL-SOLUBLE DISPERSANT, AND A BASIC REACTING METAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF METAL OXIDES, HYDROXIDES AND CARBONATES IN AN AMOUNT SUFFICIENT TO PROVIDE ABOUT 10-400 PERCENT OF ADDITIONAL METAL IN THE SAID MIXTURE HEATING THE SAID MIXTURE AT A TEMPERATURE IN THE RANGE FROM 350* F, TO 550* F, WHILE BLOWING WITH AN OXYGEN-CONTAINING GAS FOR A PERIOD FROM 5 MINUTES TO 8 HOURS UNTIL AN ALKALINE REACTING STABLE DISPERSION CONTAINING A SUBSTANTIALLY INCREASED AMOUNT OF METALS IS OBTAINED AND THEREAFTER COOLING THE REACTION PRODUCT AND REMOVING ANY UNDISPERSED SOLID MATERIAL, SAID DISPERSANT BEING SELECTED FROM THE GROUP CONSISTING OF METAL SULFONATES, METAL SALTS OF OLEFIN-PHOPHORUS SULFIDE REACTION PRODUCTS AND METAL ALKYL PHENOLATES, SAID METAL SALT, SAID BASIC REACTING METAL COMPOUND AND SAID DISPERSANT HAVING THEIR METAL COMPONENTS SELECTED FROM THE CLASS CONSISTING OF ALKALI METALS, ALKALINE EARTH METALS, LEAD, TIN AND ZINC. 